CN111978349B - Method for synthesizing phosphonimide compound - Google Patents
Method for synthesizing phosphonimide compound Download PDFInfo
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- CN111978349B CN111978349B CN202011018730.6A CN202011018730A CN111978349B CN 111978349 B CN111978349 B CN 111978349B CN 202011018730 A CN202011018730 A CN 202011018730A CN 111978349 B CN111978349 B CN 111978349B
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- amide derivative
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 30
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 52
- 239000003960 organic solvent Substances 0.000 claims abstract description 48
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 78
- 125000001424 substituent group Chemical group 0.000 claims description 34
- 230000035484 reaction time Effects 0.000 claims description 17
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229960002089 ferrous chloride Drugs 0.000 claims description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 11
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- -1 azide compound Chemical class 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical class NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KTOQRRDVVIDEAA-UHFFFAOYSA-N 2-methylpropane Chemical compound [CH2]C(C)C KTOQRRDVVIDEAA-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003800 Staudinger reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005447 aza-Wittig reaction Methods 0.000 description 1
- PJHUABJTDFXYRQ-UHFFFAOYSA-N benzoyl azide Chemical compound [N-]=[N+]=NC(=O)C1=CC=CC=C1 PJHUABJTDFXYRQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- DHOUOTPZYIKUDF-UHFFFAOYSA-N imino(triphenyl)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=N)C1=CC=CC=C1 DHOUOTPZYIKUDF-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms
- C07F9/655345—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having sulfur atoms, with or without selenium or tellurium atoms, as the only ring hetero atoms the sulfur atom being part of a five-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The method relates to a method for synthesizing a phosphinimide compound, and belongs to the field of metal catalytic organic synthesis. A method for synthesizing phosphinimide compounds comprises the following steps: adding the N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and performing post-treatment after the reaction is finished to obtain the phosphinimide compound. The method for synthesizing the phosphinimide compound disclosed by the invention has the following beneficial effects: (1) wide substrate range; (2) the catalyst is relatively low in price and less in dosage; (3) the reaction operation is simple; (4) The reaction yield is higher, and the higher yield can still be obtained when the reaction is amplified to gram level.
Description
Technical Field
The method relates to a method for synthesizing a phosphinimide compound, and belongs to the field of metal catalytic organic synthesis.
Background
The phosphonimide compound is an important organic synthesis intermediate, has a nitrogen-phosphine double bond structure, and has wide application in aza-Wittig (Wittig) reaction. Meanwhile, the phosphorus atom of the compound contains lone pair electrons, and can be coordinated with metal to be used as a guide group to realize the regioselective functionalization of C-H bond. Therefore, the synthesis of the compounds has very important significance, and a plurality of synthesis methods are continuously emerged.
In a classical Staudinger reaction, an azide compound and a tertiary phosphine (e.g., ph) 3 P) reacting to generate a phosphonyl imine intermediate which is unstable and is hydrolyzed to obtain the corresponding amine. When the N atom contains acyl, the stability of the compound is greatly enhanced, and the compound can be conveniently separated and used for subsequent reactions。
In 2005, calitzky et al disclosed a method of synthesizing N-acylphosphinimides (Helvetica Chimica Acta,2005,88 (7), 1664-1675) using an acyl azide compound and triphenylphosphine as reactants. The reaction formula is as follows:
froeyen et al, 1993, disclose a method for synthesizing phosphinimide compounds from benzoyl chloride, triphenylphosphine and sodium azide (phosphorous, sulfur and Silicon and the Related Elements,1993,78 (1-4), 161-71), wherein benzoyl chloride and sodium azide are used as starting materials to generate acyl azide in situ, and then the acyl azide reacts with triphenylphosphine to obtain phosphinimide. The reaction formula is as follows:
in 1988, cristau et al disclosed a method for synthesizing N-acylphosphinimide compounds from triphenylphosphine imide and ethyl benzoate (Tetrahedron Letters,1988,29 (32), 3931-3934). The reaction formula is as follows:
in 1984, laszlo et al disclosed a method for synthesizing phosphinimide compounds by using benzoyl hydrazine derivatives and triphenylphosphine as raw materials through multi-step reactions (Tetrahedron Letters,1984,25 (41), 4651-4654). In the method, benzoyl hydrazine is firstly generated into benzoyl azide under the action of Clayfen and then reacts with triphenylphosphine to generate phosphinimide. The reaction formula is as follows:
as described above, many reports have been made on the synthesis of phosphinimides. However, the disclosed methods usually require the use of explosive azide compounds as raw materials or intermediates, which has great safety hazards and limits the research and application of the phosphonimide.
Therefore, the need of continuous research for developing novel and efficient synthesis methods of the phosphonimide still exists, and therefore, the invention provides a method for synthesizing the phosphonimide compounds, which has the advantages that the raw materials for reaction are simple and easy to obtain, and a series of phosphonimide compounds are synthesized mildly and efficiently by using cheap metallic iron as a catalyst.
Disclosure of Invention
The invention aims to: in order to solve the defects of the prior art, the invention provides a simple and efficient method for synthesizing the phosphinimide compound, the method does not use the azide compound as the raw material, has simple reaction process, cheap catalyst and high yield, and can still obtain higher yield when the phosphinimide compound is amplified to gram-scale.
The technical scheme is as follows: a method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1 to 2:0.01 to 0.1;
the dosage of the organic solvent is 5 to 20ml/mmol based on the molar weight of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is C1-C10 alkyl, phenyl, substituted phenyl, naphthyl or heterocycle, wherein:
the substituent group in the phenyl group containing the substituent group comprises one or more of C1-C10 alkyl, alkoxy, halogen, nitro and trifluoromethyl;
heterocycles include pyridine, furan, thiophene;
R 2 is one of methyl, ethyl, propyl, butyl, phenyl and benzyl;
R 3 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 4 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 5 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl, wherein:
the substituent in the phenyl containing the substituent is one of C1-C6 alkyl, alkoxy, halogen, nitro and trifluoromethyl.
Further, the organic solvent is any one of methanol, ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, petroleum ether and ethyl acetate.
Still further, the organic solvent is dichloroethane.
Further, the catalyst is any one of cuprous chloride, cuprous trifluoromethanesulfonate, ferrous chloride, ferrous acetate, ferrous sulfate heptahydrate and ferric chloride.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction is 0.5-12 h.
Further, the reaction time of the reaction was 1h.
Further, the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.2:0.05.
the method for synthesizing the phosphinimide compound has the following advantages that:
(1) The range of the substrate is wide;
(2) The catalyst is relatively low in price and less in dosage;
(3) The reaction operation is simple;
(4) The reaction yield is high, and the yield can still be obtained when the reaction is amplified to gram level.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention.
The invention discloses a method for synthesizing a phosphinimide compound, which comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1 to 2:0.01 to 0.1;
the dosage of the organic solvent is 5 to 20ml/mmol based on the molar weight of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is C1-C10 alkyl, phenyl, substituted phenyl, naphthyl and heterocycle, wherein:
the substituent group in the phenyl group containing the substituent group comprises one or more of C1-C10 alkyl, alkoxy, halogen, nitro and trifluoromethyl;
heterocycles include pyridine, furan, thiophene;
R 2 is one of methyl, ethyl, propyl, butyl, phenyl and benzyl;
R 3 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 4 is phenyl, containing substituentsOne of phenyl and C1-C10 alkyl;
R 5 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl, wherein:
the substituent in the phenyl containing the substituent is one of C1-C6 alkyl, alkoxy, halogen, nitro and trifluoromethyl.
The reaction formula is as follows:
the organic solvent is any one of methanol, ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, petroleum ether and ethyl acetate, and preferably dichloroethane.
The catalyst is any one of cuprous chloride, cuprous trifluoromethanesulfonate, ferrous chloride, ferrous acetate, ferrous sulfate heptahydrate and ferric chloride, and is preferably ferrous chloride.
Further, the reaction time of the reaction is 0.5 to 12 hours, and may be 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, preferably 1 hour.
The room temperature range in this application is 0 to 35 ℃, and may be 0 ℃,5 ℃, 10 ℃, 15 ℃,20 ℃,25 ℃, 30 ℃, 35 ℃ and the like.
Example 1
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 92 percent, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.2:0.05;
the amount of the organic solvent is 10ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is phenyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1 H NMR(400MHz),8.41(d,J=8.0Hz,2H),7.91-7.87(m,6H),7.60-7.57(m,3H),7.52-7.42(m,9H)pp。
example 2
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 86%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:2:0.1;
the amount of the organic solvent is 5ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is p-tolyl;
R 2 is a tertiary butyl group; (ii) a
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is methanol.
Further, the catalyst is cuprous chloride.
Further, the reaction time of the reaction was 12h.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1H NMR(400MHz,CDCl 3 )δ8.24(d,J=8.0Hz,2H),7.99–7.70(m,6H),7.66–7.51(m,3H),7.47(td,J=7.4,3.0Hz,6H),7.20(d,J=8.0Hz,2H),2.39(s,3H).
example 3
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 70%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.01;
the amount of the organic solvent is 20ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is p-chlorophenyl;
R 2 is a tertiary butyl group;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is ethanol.
Further, the catalyst is cuprous trifluoromethanesulfonate.
Further, the reaction time of the reaction was 0.5h.
The product of this example was subjected to nuclear magnetic resonance, and the results were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.27(d,J=8.4Hz,2H),7.81(m,,6H),7.55(dd,J=7.5,6.1Hz,3H),7.47(m,6H),7.34(d,J=8.4Hz,2H).
example 4
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 85%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.5:0.8;
the amount of the organic solvent is 15ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is naphthyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is acetonitrile.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 2h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.87(s,1H),8.43(dd,J=8.6,1.5Hz,1H),7.96(d,J=7.4Hz,1H),7.93–7.77(m,8H),7.58(m,3H),7.54–7.42(m,8H).
example 5
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 78%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.2:0.02;
the amount of the organic solvent is 5ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is p-bromophenyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous acetate.
Further, the reaction time of the reaction was 3h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.20(d,J=8.4Hz,2H),7.82(m,6H),7.56(m,3H),7.49(m,8H).
example 6
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 85%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:2:0.8;
the amount of the organic solvent is 8ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is p-methoxyphenyl;
R 2 is a tertiary butyl group;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is tetrahydrofuran.
Further, the catalyst is ferrous sulfate heptahydrate.
Further, the reaction time of the reaction was 10 hours.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.30(d,J=8.8Hz,2H),7.91–7.72(m,6H),7.62–7.52(m,3H),7.47(m,6H),6.90(d,J=8.8Hz,2H),3.84(s,3H).
example 7
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.1;
the amount of the organic solvent is 16ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is p-cyanophenyl;
R 2 is a tertiary butyl group;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloromethane.
Further, the catalyst is ferrous sulfate heptahydrate
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.40(s,2H),7.82(s,6H),7.73–7.41(m,11H).
example 8
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 85%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.6:0.5;
the amount of the organic solvent is 15ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is m-fluorophenyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is petroleum ether.
Further, the catalyst is ferric chloride.
Further, the reaction time of the reaction was 0.75h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.09(d,J=7.7Hz,1H),8.07–7.99(m,1H),7.90–7.76(m,6H),7.58(td,J=7.2,1.4Hz,3H),7.54–7.44(m,6H),7.35(td,J=7.9,5.7Hz,1H),7.13(td,J=8.3,2.3Hz,1H).
example 9
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in an air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with a yield of 65%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.01;
the amount of the organic solvent is 10ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is m-chlorophenyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is ethyl acetate.
Further, the catalyst is ferric trichloride.
Further, the reaction time of the reaction was 2h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.33(s,1H),8.18(d,J=7.7Hz,1H),7.89–7.75(m,6H),7.57(dd,J=7.6,5.9Hz,3H),7.49(td,J=7.5,3.0Hz,6H),7.41(d,J=7.9Hz,1H),7.32(t,J=7.8Hz,1H).
example 10
A method for synthesizing phosphinimide compounds comprises the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 92%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.5:0.05;
the amount of the organic solvent is 10ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is 3, 5-dimethylphenyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows: 1 H NMR(400MHz,CDCl 3 )δ7.96(s,2H),7.90–7.76(m,6H),7.55(m,3H),7.47(m,6H),7.08(s,1H),2.36(s,6H).
example 11
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding the N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and performing post-treatment after the reaction is finished to obtain the phosphinimide compound, wherein the yield is 87 percent:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1:0.06;
the amount of the organic solvent is 5ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is m-tolyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is methanol.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ8.16(d,J=8.8Hz,2H),7.89–7.76(m,6H),7.55(td,J=7.2,1.4Hz,3H),7.47(m,6H),7.33–7.26(m,2H),2.39(s,3H).
example 12
A method for synthesizing a phosphinimide compound, comprising the steps of:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting at room temperature in an air atmosphere, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound with the yield of 92%, wherein:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1.5:0.05;
the amount of the organic solvent is 15ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is 2-thienyl;
R 2 is tert-butyl;
R 3 is phenyl;
R 4 is phenyl;
R 5 is phenyl.
Further, the organic solvent is dichloroethane.
Further, the catalyst is ferrous chloride.
Further, the reaction time of the reaction was 1h.
The product of this example was subjected to nuclear magnetic resonance, and the results of product detection were as follows:
1 H NMR(400MHz,CDCl 3 )δ7.83(m,6H),7.77(d,J=3.0Hz,1H),7.56(m,3H),7.48(m,6H),7.38(d,J=4.9Hz,1H),7.08–6.99(m,1H).
examples 13 to 31
Is essentially the same as example 1, except that the substituent R 1 The following table specifically shows the differences:
examples 32 to 38
Is substantially the same as example 2, except that the substituent R 2 The following table specifically shows the differences:
R 2 | |
example 32 | Methyl radical |
Example 33 | Ethyl radical |
Example 34 | Isopropyl group |
Example 35 | N-propyl radical |
Example 36 | N-butyl |
Example 37 | Phenyl radical |
Example 38 | Benzyl radical |
Examples 39 to 56
Is essentially the same as example 3, except that the substituent R of the tertiary phosphine 3 The following table specifically shows the differences:
R 3 | |
example 39 | Phenyl having a substituent which is methyl |
Example 40 | Phenyl having a substituent which is ethyl |
EXAMPLE 41 | Phenyl having a substituent being n-heptyl |
Example 42 | Phenyl containing a substituent being methoxy |
Example 43 | Phenyl having a substituent of F |
Example 44 | Phenyl containing a substituent, the substituent being Cl |
Example 45 | Phenyl containing a substituent being nitro |
Example 46 | Phenyl having a substituent which is trifluoromethyl |
Example 47 | Methyl radical |
Example 48 | Ethyl radical |
Example 49 | Isopropyl group |
Example 50 | Isobutyl radical |
Example 51 | Isoamyl radical |
Example 52 | N-hexyl radical |
Example 53 | N-heptyl radical |
Example 54 | N-octyl radical |
Example 55 | N-nonyl radical |
Example 56 | N-decyl radical |
Examples 57 to 74
Is essentially the same as example 4, except that the substituent R of the tertiary phosphine 4 The following table specifically shows the differences:
examples 75 to 92
Is essentially the same as example 5, except that the substituent R of the tertiary phosphine 5 The following table specifically shows the differences:
the embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (7)
1. A method for synthesizing a phosphinimide compound is characterized by comprising the following steps:
adding an N-hydrocarbon acyloxy amide derivative, tertiary phosphine, a catalyst and an organic solvent into a reaction container, reacting in the air atmosphere at room temperature, and carrying out post-treatment after the reaction is finished to obtain a phosphinimide compound, wherein:
the reaction formula is as follows:
the mol ratio of the N-hydrocarbon acyloxy amide derivative to the tertiary phosphine to the catalyst is 1:1 to 2:0.01 to 0.1;
the dosage of the organic solvent is 5 to 20ml/mmol based on the molar amount of the N-hydrocarbon acyloxy amide derivative;
the structural formula of the N-hydrocarbon acyloxy amide derivative is shown in the specificationWherein:
R 1 is C1-C10 alkyl, phenyl, substituted phenyl, naphthyl, heterocycle,
wherein:
the substituent in the phenyl containing the substituent is one or more of C1-C10 alkyl, alkoxy, halogen, nitro and trifluoromethyl;
the heterocyclic ring is pyridine, furan or thiophene;
R 2 is one of methyl, ethyl, propyl, butyl, phenyl and benzyl;
R 3 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 4 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl;
R 5 is one of phenyl, phenyl containing substituent groups and C1-C10 alkyl, wherein:
the substituent group in the phenyl containing the substituent group is one of C1-C6 alkyl, alkoxy, halogen, nitro and trifluoromethyl, wherein:
the catalyst is any one of cuprous chloride, cuprous trifluoromethanesulfonate, ferrous chloride, ferrous acetate, ferrous sulfate heptahydrate and ferric chloride.
2. The method of claim 1, wherein the organic solvent is any one of methanol, ethanol, acetonitrile, dichloroethane, tetrahydrofuran, dichloromethane, petroleum ether, and ethyl acetate.
3. The method of claim 2, wherein the organic solvent is dichloroethane.
4. The method of claim 1, wherein the catalyst is ferrous chloride.
5. The method for synthesizing phosphinimide compounds according to claim 1, wherein the reaction time is 0.5 to 12 hours.
6. The method for synthesizing phosphinimide compounds according to claim 5, wherein the reaction time is 1h.
7. The method of claim 1, wherein the molar ratio of N-hydrocarbonacyloxy amide derivative, tertiary phosphine, catalyst is 1:1.2:0.05.
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